Treatment of hydrocarbons with radioactive materials



v .1. September, i938. Serial N0. 232,127

This invention relates to the production of ocerite. erdmannite, erikite, eschynite, eucrasite,

, valuable resinous materials, synthetic resins, film euxenite, hydrothorite, kochelite, mackintoshite,

forming materials and plastic materials particmaitlandit'e. monazite sand, naeglite, nicolayit-e, ularly useful as rubber substitutes. The inven= orangite, pilbarite, steenstrupine thorianite, tion is particularly concerned with a process of s thorlte, thorogummite, thorotungstite, thucholite, polymerization of unsaturated materials. uraninite, urananiobite, yttrialite, yttrocrasite,

This invention is also concerned with procan be employed as can radioactive thorium duction of chlorinated materials useful as a sub compounds as a radioactive dioxide. Uranium stitute for rubbenas resins, in coating composiand radium materials are also useful includtions, paints and the like. The materials of the i ins ampangabeite, autunite, bassetlte, becquerpresent invention are characterized by certain lite, betafite. blomstrandine, brannerite, carphysical characteristics which render them parnabite, clarkeite, curite, davidite, dewendtite,

ticularly desirable. in surface coating composidumantite, ellsworthtite, ferghanite, fergutions, being non-tacky, stable, acidand alkalisonite, fourmarierite, gummite, hatchettalite, resistant. hielmite, ianthinite, ishikawaite, johannite, kaso- I'he present invention can be practiced on lite, medjidite, mendelyeevite, metatarbermite, pure unsaturated hydrocarbons available as inmetazeunenite, nivenite, parsonsite, phosphurinvidual hydrocarbons. I have also successfully anylite, pilbarite, plumbaniobite, polycrase, pripracticed the invention on hydrocarbon mixtures orite, randite, renardite, rutherfordite, samarswhich included unsaturated hydrocarbons as olekite. samiresite, schroeckeringite, slglodowskite, fins as wellas other hydrocarbons as paraflins. soddyite, torbernite, trogerite, uraconite, uranaromatics and naphthenes although the first two ni r nlni e. ur n ch lcl lir 111 were preponderantly present. uranoniobite, uranophane, uranopilite, menu- It is in general the broad object of the present spathite, uranosphaerite, uranospinite, uraninvention to provide a novel process for the athallite, uvanite, voglite, walpurgite, zeunerite production of a resinous material particularly and zippeite. a chlorinated material of high stability.

Another object of the present invention is to the radioactive properties .of these materials; provide for the production of a stable, non-tacky their use is to be distinguished because of dechlorinatd resin. 7, V pendence on this property in these material Another object of the present invention is to which I employ as polymerization and/or conprovide a process for polymerizing the unsaturate densation and/or hydrogenation and/or dehydrocontent of a hydrocarbon mixture containing genation catalysts. Because-of the complexnature olefins and paraflins and possibly aromatics and of the materials and reactions I cannot say at naphtha-133, this time what is the exact nature or mechanism Another object is to provide a process for polyof the reactions invplved and one or more prob merizi'ng and condensing the unsaturated and ably occur concurrently or successively during the saturated content of a hydrocarbon mixthe period that thehydrocarbon mixture is unture of which various petroleum oils are typical. dergoing treatment or is in contact with or is f The invention includes other objects and feaso exposed to action of the catalytic material. tures of advantage, some of which. togetherwith The polymerizing agent becomes inactive, ap-

. the foregoing, will appear hereinafter wherein I parently by on an acid condition from the have set forth by way of example and not by way oil because 2 have found that by washing 'with of limitation, the present preferred mer of an alkaline wash the agent is again rendered efpracticing the process of, my invention to profective although its life is usually'fairly long. duce the desirable chlorinated material of the g l8 present invention. p

In producing the material of the present inone h us nd parts of a ulf c s naphthene vention I have found it desirable to polymerize base coma-111MB 8 y 0 8 8 nd par fand condense a mixture of pa and oleflns, fins were mixed wi h 30 parts of fuller's earth such as can be found in a petroleum oil, by treat 8 carrier and 81111808 extender 1'9 10 P rt ment with a radioactive material particularly of of radioactiye thorium dioxide. The oil had a ,the thorium series. In place of thorium as such, viscosity of seconds Saybolt Universal and radioactive materials, includim thorium are usecuntained f atu ated hydrocarbf'ls. ful as auerlite, bragserite, calcio-thorite, cary- 66 and had a specific gravity of 28 Baum. The

So far as I am aware Iam the first to employ we re 'mixed'with 40 parts carrier andyl parts-of radioactiv thorium di-' Wl'rile"the-;mixture was maintained at mixture was heated to 265 F. for 30 minutes--with' agitation. Twenty parts of trichloroethyiene were added and the mixture agitated for""rninutes, then filtered. This treatment was given the material to effect olefin polymerization therein. This product contained valuable resinous products, film forming materials and plastics.

The mixture was then chlorinated to efiect addition chlorination. Any process can be employed to efiect this but I prefer a liquid phase operation. Chlorine was passed through the filtrate until it had increased over 60% in weight and preferably about 65% by weight. In the rated chlorinated hydrocarbons, both chain and ring, including aliphaticand aromatic compresence of the trlchlorethylene, the chlorine acts as if in the liquid phase, the chlorine being dissolved in the oil miscible trichloiethylene. The mixture was then permitted-to stand until a heavy precipitate had se ated out as a heavy syrupy mass. This require about '72 hours. The

top layer was largely constituted of the liquid saturated hydrocarbon while the bottom layer contained the materials of the present invention.

Onepqrtion of the bottom layer was distilled ir Va-a1 fi -and a tough rubbery mass of specific gravity 1.5 and of alight amber color was'obtaine d. This mass was a combination of about 94.5% of a rubbery hydrocarbon mixed with oils and resins to make up the remainder, the mixture containing a trace of thorium dioxide. This material was insoluble in petroleum hydrocarbons of thenature of gasoline, painters naphtha,

and alcohols, but was soluble in chlorinated hydrocarbons and coal tar solvents, benzene, toluene and'the like. v

The second portion of the bottom layer, a liquid. having a viscosity of 500 seconds Saybolt Universal, was painted as a'thin film on metal.

the air in several minutes to touch.

film, when dry, was resistant to commerfl al muriatic acid, 50% sulphuric acid, satuted solutions of trisodiumphosphate, sodium riea i a, a

liquid produced is non hygroscopic and is he'a y,is yrupy and amber in color, of 1.54 avity(66 F.) and 9.613 pounds per ts iodine number and saponification zero, while the vacid number dissolved in: 'ienzolg-is 2. ,BecauseGotcharacteristics it is ble-ias a transformer oil, its dielectric strengthis equiiralent'to that of 25,000 volt oil; it"is fire resisting, charrin'g 480? F;

Example 2 :Two thousand parts of a Qalifornia fuel oil .rullers earthas a oxide. 4 225 F. 'it' jzwa stirred for an hour. After this it was filtered." 'Ien per cent by weight of triand decomposing at 65 The material to be polymerized can be varied and I have successfully treated the bottom fraction remaining after recovery and separation of a gasoline from a liquid formed by the usual and known phosphoric acid polymerization of a mixture of olefins after the -manner described by Ipatiefi (Ind. & Eng. Chem. 27, .1077, 1935). This bottom fraction, composed of about 20%-25% oleflns and about 20% aromatics with the remainder largely para'filrrs, was treated with a monazite sand catalyst at about 225 F. for several hours, usually about two hours and at about 150- p'ounds pressure. The fractionhad-an initial boiling point of 346 R, an endpoint of 625 1 Rand a gravity of about 22 A. P. I. on the average.

The polymerization treatment resultsin alteration of the initial fraction. Depending on the period of -treatment a 10%-20% solid fraction is produced, the remainder beingliquid. The

'solid is hard, black and resinous; it is useful as a paint base, particularly heat resistant punts, as a core oil additive when dissolved in a suitable solvent. ,The liquid fraction can be distilled into various useful fractions useful-as solvents, paint thinners, drying oils,.wetting materials,- as lubricating oils, as coating compositions suitable for direct application to surfaces, parti larly metal surfaces, as "well as sources of ther chemicals.

A lubricating oil fraction can-- bolt at 130F. and 44 at 210 F., anda viscosity index of 45 was recovered.- This oil had desirable lubricating and "oiliness. characteristics.

irfietas'ilicateypaint removers, sodium hyroxidejethyl alcohol, gasoline, and painters soluble. It contains about 20.4% solids,

chloroethylene was added and chlorine gas passed through the filtrate until weight increasev had occurred. This mixture was allowed to stand about 72 hours, at the end of which time 32% of the mixture had settled to the bottom as a heavy syrupy layer; .{Ihis .-layer was drawn off, its properties and qualities being much the same as those discussed under Example 1, being, as with the liquid product of Example 1, soluble. in acetone, xylol, benzol, hifiash naphtha, the usual ketone solvents, secondary butyl acetate, butyl I have found the polymerized material should be chlorinated in the liquid phase, either with a body of liquid-chlorine or with chlorine carried in a suitable chlorine solventso that the oil chlorinates as in the liquid phase.

I have discovered that if the chlorination operation be conducted in the presence of 'a saturated chlorinated hydrocarbon such as-trichloroethylene, ethylene dichloride, propylene dichloride, carbon tetrachloride, chloroform, methyl chloride'or a chlorinated saturated aromatic hydrocarbon as a dichlor benzene or a hydrocarbonin which the chlorine present has been-acquiredby way of substitution and not by way of addition, the production of tacky, sticky and relatively unstable products is avoided. Instead the air-drying, non-tacky relatively stable prod uct of the present invention results.

I have further found that to secure-the maximum effect from the chlorinated solvent it is highly desirable that the temperature of chloriexample, when subjected to strong acid and alkali.

cellosolve, ethylene dichloride, and other atu- 755 While I have previously mentionedthat a small amount of the hydrocarbon is employed, usually recovered i, from the product. For example, a neutral, lemon colored oil having a viscosity of 98 seconds Sayaesueso about this is only by way of illustration and either more or less of the solvent can be employed. For example, I have utilized as much as of the solvent and as little as 1% without harmful eiiects in the case of employing the larger percentage and without losing the beneficial efiect in the case of the smaller percentage. However, it is preferred that the operation be conducted with about 10% of the material present.

If a portion of the amber syrupy liquid resultihg from the chlorination is mixed with an alcohol. for example, ethyl alcohol, a pearly white mass eoagulates instantly. When the alcohol is separated, the pearly mass remains. it is slightly tacky but airdries fairly rapidly The hydrocarbon mixture undergoing polymerization can be advantageously subject to oxidation to increase production of oxygen containing compounds therein, particularly carboxylic acids. To achieve this air, or other oxygen containing gas, is introduced into the hydrocarbon material. I have found the proportion of a pound of air per pound of hydrocarbon material preierable, giving a high increase in organic acid content and providing a source material from which ketones and esters can be manufactured readily.

The bottoms remaining after gasoline removal from a liquid formed by phosphoric acid polymeriuation oi oleiins in a cracked refinery gases were polymerized and treated according to the process of this invention. One hundred fifteen pounds were held for about two hours at 220 pounds at NEW-250 F. The pressure can go as low as BOpounds but a longer time is required.

; release inert nitrogen and unreacted air.

it is. neither reasonable to demand that an inventor know all of the art at the present time upon. which he may supposedly-but erroneously so-select the words of this disclosure nor possible for any human to anticipate what direction the future development of the art may take, which may make the language here used inapt. Therefore, the disclosure of this invention should not be construed as limited by mere interpretation of the words used. It is contemplated that changes in form may be made with variations and departures from. the illustrated examples without departing from the scope of this invention. Such variations and departures include those made possible by the discovery of improved materials and better uses and forms of present materlals, as well as practices and results which may be possible in fabrication and handling.

I claim: 7 '1. A process for treatment or a hydrocarbon mixture rich in olefins and aromatics comprising maintaining said mixture in contact with a finely divided radioactive material as substantially the sole efiective catalyst at an elevated non-cracking-temperature to effect polymerization and condensation in said mixture.

2. A process for treatment of a hydrocarbon mixture rich in oleiins and aromatics comprising maintaining said mixture incontact with a finely divided radioactive material as substantially the sole .ei'fective catalyst while subjecting said mixture to exudation; at an elevated non-cracks 'ing temperature .to eflect polymerization and condensation in said mixture.

3. A process for treatmbnt of a. hydrocarbon mixture rich in olefins and aromatics comprising maintaining said mixture in contact with a finely divided radioactive material as substantially the sole effective catalyst while subjecting said mixture toWdation with about an equafi? weight of air at an elevated non-cracking temperature to elfect polymerization and condensation in said mixture.

d. A process for production-oi valuable materials comprising polymerizing a mixture of olefin and aromatic hydrocarbons in the presence of a radioactive material as the only elifective polymerization catalyst present to give a liquid having a final boiling point of about 625 F distilling c5 of said liquid a fraction boiling over the range 346 F.-625 It, and further polymerizing said distilled fraction to produce a polymerized fraction containing about 20% solids.

5. A process for production of valuable materials comprising polymerizing a mixture of olefin and aromatic hydrocarbons as the only effe tivepolymerization catalyst present to give a liquid having a final boiling point of about 525 lit, distilling ofi of said liquid a fraction boiling over the range 346 F.-625 F., and further polymerizing said distilled fraction until it contains about 20% solids, and simultaneously oxidizing said polymerized fraction.

6. A process for producing valuable materials comprising polymerizingin the presence of a monazite sand as the only effective polymerization catalyst a liquid fraction having a boiling point range of about 346 F. to 625 F. and containing about 20% olefins and 20% aromatics at about pounds pressure and at about 225 F. for about two hours.

7L A process for production of valuable materials from olefin and aromatic hydrocarbon mixture comprising maintaining said material at a temperature of about F. to about 265 F. for about a half hour to two hours in the presence oil a finely divided radioactive material as substantially the only efiective catalytic material present.

8. A process for production of valuable materials from olefin and aromatic hydrocarbon mixture comprising-maintaining said material at a temperature of about 160 F. to about 265 F.

.for about a. half hour to two hours in the presence of a finely divided radioactive material as substantially the only effective catalytic material present and admitting an oxygen carrying gas into said mixture to oxidize at least some components thereof.

. 9. A process for production of valuable materials from olefin and aromatic hydrocarbon mixture comprising maintaining a mass of said material at a temperature of about 160 F. to about 265 F. for about a half hour to two hours in the presence of a, finely divided radioactive material a substantially the only eiiective catalytic material present and slimming about an equal weight oi air as an oxygen carrying gas into acid mixture 7 to oxidize at least some components thereof. l

10. A process for production of valuable materials from a petroleum fraction heavier tmn gasoline comprising maintaining a. mass would fraction at a temperature or about 160 F. to

-'material as substantially the only-e gasoline comprising maintaining a mass of said fractionat a temperature of about-160 F.to about 265 F. for about a half hour to two hours in the presence of a finely dividedi radioactive ecti ve catalytic' material present and admitting an oxygen carrying gas into said mixture to oxidize at least some components thereof.

12. A- process for production of valuable materials from a petroleum fraction heavier than in assasso gasoline coinprising maintaining a mass of said fraction at a temperature of about 160 F. to about 265 F; for about a half hour to two hours in'the presence of a finely divided radioactive material as substantially the only effective cata- -lytic material present and admitting' about an equal weight of air as an oxygen carrying gas into said mixture to oxidize at least some components thereof. 

